Polyether polymerization process

Abstract

Alkylene oxides are polymerized in the presence of a catalyst system that includes a double metal cyanide catalyst that is modified with certain metal or semi-metal compounds. At least one additive is present. The additive is an alkali metal, ammonium or quaternary ammonium salt of a monocarboxylic acid having up to 24 carbon atoms; monobasic potassium phosphate, a monobasic ammonium or quaternary ammonium phosphate, a dibasic ammonium and quaternary ammonium phosphate or phosphoric acid.

1 . A method for producing a polyether, the method forming a reaction mixture comprising a hydroxyl-containing starter, at least one alkylene oxide, a catalyst complex, and an additive, and polymerizing the alkylene oxide onto the hydroxyl-containing starter to produce the polyether, wherein the catalyst complex is selected from the group consisting of catalyst complexes I and II, wherein
 catalyst complex I is a catalyst complex produced in a method comprising:   a) forming a starting solution comprising i) a solvent that includes at least one of water and a liquid aliphatic alcohol, the solvent having dissolved therein ii) a cyanometallate compound having an M 2  metal cyanometallate group and iii) a M 1  metal compound which reacts with the cyanometallate compound to form a water-insoluble M 1  metal cyanometallate, which starting solution further contains 0.01 to 10 moles, per mole of cyanometallate compound, of iii) at least one M 5  metal or semi-metal compound different from the M 1  metal salt, the M 5  metal or semi-metal compound being a compound of a M 5  metal or semi-metal and an anion, the M 5  metal or semi-metal being selected from one or more of magnesium, a Group 3-Group 15 metal or semi-metal, or a lanthanide series metal which the M 5  metal or semi-metal is bonded to at least one alkoxide, aryloxy, carboxylate, acyl, pyrophosphate, phosphate, thiophosphate, dithiophosphate, phosphate ester, thiophosphate ester, amide, oxide, siloxide, hydride, carbamate or hydrocarbon anion, and the M 5  metal or semi-metal compound is devoid of halide anions; and   b) reacting the cyanometallate compound and M 1  metal compound to form a water-insoluble catalyst complex that includes a M 1  metal cyanometallate;   and catalyst complex II corresponds to the formula:
   M 1   b [M 2 (CN) r (X 1 ) t ] c [M 3 (X 2 ) 6 ] d ·nM 4   x A 1   y ·pM 5   w A 2   z  
 
   
       wherein:
 M 1  and M 4  each represent a metal ion independently selected from Zn 2+ , Fe 2+ , Co +2+ , Ni 2+ , Mo 4+ , Mo 6+ , Al +3+ , V 4+ , V 5+ , Sr 2+ , W 4+ , W 6+ , Mn 2+ , Sn 2+ , Sn 4+ , Pb 2+ , Cu 2+ , La 3+ , and Cr 3+ ; 
 M 2  and M 3  each represent a metal ion independently selected from Fe 3+ , Fe 2+ , Co 3+ , Co 2+ , Cr 2+ , Cr 3+ , Mn 2+ , Mn 3+ , Ir 3+ , Ni 2+ , Rh 3+ , Ru 2+ , V 4+ , V 5+ , Ni 2+ , Pd 2+ , and Pt 2+ ; 
 M 5  represents at least one magnesium, Group 3-Group 15 metal, or lanthanide series metal or semi-metal ion; 
 X 1  represents a group other than cyanide that coordinates with the M 2  ion; 
 X 2  represents a group other than cyanide that coordinates with the M 3  ion; 
 A 1  represents an anion selected from halide, nitrate, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, perchlorate, isothiocyanate, an alkanesulfonate, an arylenesulfonate and trifluoromethanesulfonate; 
 A 2  represents least one alkoxide, aryloxy, carboxylate, acyl, pyrophosphate, phosphate, thiophosphate, amide, oxide, siloxide, hydride, carbamate, or hydrocarbon anion; 
 b, c and d are each numbers that the M 1   b [M 2 (CN) r (X 1 ) t ] c [M 3 (X 2 ) 6 ] d  group is electrostatically neutral, provided that b and c each are greater than zero; 
 x and y are integers such that the metal salt M 4   x A 1   y  is electrostatically neutral; 
 r is an integer from 4 to 6; 
 t is an integer from 0 to 2; 
 n is a number from 0 and 20; 
 p is from 0.002 to 10; and 
 w and z are integers such that the metal salt M 5   z A 2   z  is electrostatically neutral, provided that w is from 1 to 4; 
 and the additive is selected from the group consisting of alkali metal, ammonium and quaternary ammonium salts of monocarboxylic acids having up to 24 carbon atoms; monobasic potassium phosphate, monobasic ammonium and quaternary ammonium phosphates, dibasic ammonium and quaternary ammonium phosphates and phosphoric acid. 
 
     
     
         2 . The process of  claim 1  wherein the M 5  metal or semi-metal is one or more of aluminum, hafnium, indium, manganese or gallium. 
     
     
         3 . The process of  claim 2  wherein the molar ratio of the M 5  metal or semi metal to M 2  and M 3  metals combined is 0.0025 to 50. 
     
     
         4 . The process of  claim 2  wherein M 1  is zinc and the cyanometallate compound is a hexacyanocobaltate compound. 
     
     
         5 . The process of  claim 2  wherein the additive is selected from the group consisting of alkali metal, ammonium and quaternary ammonium salts of monocarboxylic acids having up to 24 carbon atoms; monobasic potassium phosphate, monobasic ammonium and quaternary ammonium phosphates and dibasic ammonium and quaternary ammonium phosphates, and the additive is present in an amount of 1 to 10 times that of the catalyst complex, by weight. 
     
     
         6 . The process of  claim 2  wherein the additive is phosphoric acid and the amount of phosphoric acid is 0.001 to 0.2 times the weight of the catalyst complex. 
     
     
         7 . The process of  claim 2  wherein the alkylene oxide is ethylene oxide. 
     
     
         8 . The process of  claim 2  which is semi-batch process comprising steps of charging the catalyst complex and starter to a reaction vessel, activating the catalyst complex and thereafter adding at least a portion of the alkylene oxide to the reaction vessel containing the activated catalyst complex and starter under polymerization conditions without removal of product until all of the alkylene oxide has been added, or a continuous process comprising continuously feeding the catalyst complex, starter and alkylene oxide to a reaction vessel under polymerization conditions and continuously removing product from the reaction vessel. 
     
     
         9 . The process of  claim 2  wherein the reaction mixture has a hydroxyl content of 4.25 to 20 wt. %, especially 4.25 to 15 wt. %, based on the total weight of the reaction mixture, during at least a portion of step II. 
     
     
         10 . The process of  claim 2  wherein the the hydroxyl-containing starter has an equivalent weight of up to 75.